Surface lattice reconstruction is commonly observed in nickel-rich layered oxide battery cathode materials, causing unsatisfactory high-voltage cycling performance. However, the interplay of the surface chemistry and the bulk microstructure remains largely unexplored due to the intrinsic structural complexity and the lack of integrated diagnostic tools for a thorough investigation at complementary length scales. Herein, by combining nano-resolution X-ray probes in both soft and hard X-ray regimes, we demonstrate correlative surface chemical mapping and bulk microstructure imaging over a single charged LiNi0.8Mn0.1Co0.1O2(NMC811) secondary particle. We reveal that the sub-particle regions with more micro cracks are associated with more severe surface degradation. A mechanism of mutual modulation between the surface chemistry and the bulk microstructure is formulated based on our experimental observations and finite element modeling. Such a surface-to-bulk reaction coupling effect is fundamentally important for the design of the next generation battery cathode materials.
The dynamic information of lithium‐ion battery active materials obtained from coin cell‐based in‐situ characterizations might not represent the properties of the active material itself because many other factors in the cell could have impacts on the cell performance. To address this problem, a single particle cell was developed to perform the in‐situ characterization without the interference of inactive materials in the battery electrode as well as the X‐ray‐induced damage. In this study, the dynamic morphological and phase changes of selenium‐doped germanium (Ge0.9Se0.1) at the single particle level were investigated via synchrotron‐based in‐situ transmission X‐ray microscopy. The results demonstrate the good reversibility of Ge0.9Se0.1at high cycling rate that helps understand its good cycling performance and rate capability. This in‐situ and operando technique based on a single particle battery cell provides an approach to understanding the dynamic electrochemical processes of battery materials during charging and discharging at the particle level.
more » « less- NSF-PAR ID:
- 10238707
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- ChemSusChem
- Volume:
- 14
- Issue:
- 5
- ISSN:
- 1864-5631
- Page Range / eLocation ID:
- p. 1370-1376
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
more » « less
Abstract -
more » « less
Abstract Most research on the electrochemical dynamics in materials for high‐energy Li‐ion batteries has focused on the global behavior of the electrode. This approach is susceptible to misleading analyses resulting from idiosyncratic kinetic conditions, such as surface impurities inducing an apparent two‐phase transformation within LiNi0.8Co0.15Al0.05O2. Here, nano‐focused X‐ray probes are used to measure delithiation operando at the scale of secondary particle agglomerates in layered cathode materials during charge. After an initial latent phase, individual secondary particles undergo rapid, stochastic, and largely uniform delithiation, which is in contrast with the gradual increase in cell potential. This behavior reproduces across several layered oxides. Operando X‐ray microdiffraction (‐XRD) leverages the relationship between Li content and lattice parameter to further reveal that rate acceleration occurs between Li‐site fraction (
x Li) ≈0.9 and ≈0.5 for LiNi0.8Co0.15Al0.05O2. Physics‐based modeling shows that, to reproduce the experimental results, the exchange current density (i 0) must depend onx Li, and thati 0should increase rapidly over three orders of magnitude at the transition point. The specifics and implications of this jump ini 0are crucial to understanding the charge‐storage reaction of Li‐ion battery cathodes. -
All-solid-state batteries (ASSBs) have garnered increasing attention due to the enhanced safety, featuring nonflammable solid electrolytes as well as the potential to achieve high energy density. 1 The advancement of the ASSBs is expected to provide, arguably, the most straightforward path towards practical, high-energy, and rechargeable batteries based on metallic anodes. 1 However, the sluggish ion transmission at the cathode-electrolyte (solid/solid) interface would result in the high resistant at the contact and limit the practical implementation of these all solid-state materials in real world batteries. 2 Several methods were suggested to enhance the kinetic condition of the ion migration between the cathode and the solid electrolyte (SE). 3 A composite strategy that mixes active materials and SEs for the cathode is a general way to decrease the ion transmission barrier at the cathode-electrolyte interface. 3 The active material concentration in the cathode is reduced as much as the SE portion increases by which the energy density of the ASSB is restricted. In addition, the mixing approach generally accompanies lattice mismatches between the cathode active materials and the SE, thus providing only limited improvements, which is imputed by random contacts between the cathode active materials and the SE during the mixing process. Implementing high-pressure for the electrode and electrolyte of ASSB in the assembling process has been verified is a but effective way to boost the ion transmission ability between the cathode active materials and the SE by decreasing the grain boundary impedance. Whereas the short-circuit of the battery would be induced by the mechanical deformation of the electrolyte under high pressure. 4 Herein, we demonstrate a novel way to address the ion transmission problem at the cathode-electrolyte interface in ASSBs. Starting from the cathode configuration, the finite element method (FEM) was employed to evaluate the current concentration and the distribution of the space charge layer at the cathode-electrolyte interface. Hierarchical three-dimensional (HTD) structures are found to have a higher Li + transfer number (t Li+ ), fewer free anions, and the weaker space-charge layer at the cathode-electrolyte interface in the resulting FEM simulation. To take advantage of the HTD structure, stereolithography is adopted as a manufacturing technique and single-crystalline Ni-rich (SCN) materials are selected as the active materials. Next, the manufactured HTD cathode is sintered at 600 °C in an N 2 atmosphere for the carbonization of the resin, which induces sufficient electronic conductivity for the cathode. Then, the gel-like Li 1.4 Al 0.4 Ti 1.6 (PO 4 ) 3 (LATP) precursor is synthesized and filled into the voids of the HTD structure cathode sufficiently. And the filled HTD structure cathodes are sintered at 900 °C to achieve the crystallization of the LATP gel. Scanning transmission electron microscopy (STEM) is used to unveil the morphology of the cathode-electrolyte interface between the sintered HTD cathode and the in-situ generated electrolyte (LATP). A transient phase has been found generated at the interface and matched with both lattices of the SCN and the SE, accelerating the transmission of the Li-ions, which is further verified by density functional theory calculations. In addition, Electron Energy Loss Spectroscopy demonstrates the preserved interface between HTD cathode and SEs. Atomic force microscopy is employed to measure the potential image of the cross-sectional interface by the peak force tapping mode. The average potential of modified samples is lower than the sample that mix SCN and SEs simply in the 2D planar structure, which confirms a weakened space charge layer by the enhanced contact capability as well as the ion transmission ability. To see if the demonstrated method is universally applicable, LiNi 0.8 Co 0.1 Mn 0.1 O 2 (NCM811) is selected as the cathode active material and manufactured in the same way as the SCN. The HTD cathode based on NCM811 exhibits higher electrochemical performance compared with the reference sample based on the 2D planar mixing-type cathode. We believe such a demonstrated universal strategy provides a new guideline to engineer the cathode/electrolyte interface by revolutionizing electrode structures that can be applicable to all-solid-state batteries. Figure 1. Schematic of comparing of traditional 2D planar cathode and HTD cathode in ASSB Tikekar, M. D. , et al. , Nature Energy (2016) 1 (9), 16114 Banerjee, A. , et al. , Chem Rev (2020) 120 (14), 6878 Chen, R. , et al. , Chem Rev (2020) 120 (14), 6820 Cheng, X. , et al. , Advanced Energy Materials (2018) 8 (7) Figure 1more » « less
-
more » « less
Abstract Crystallographic defects exist in many redox active energy materials, e.g., battery and catalyst materials, which significantly alter their chemical properties for energy storage and conversion. However, there is lack of quantitative understanding of the interrelationship between crystallographic defects and redox reactions. Herein, crystallographic defects, such as geometrically necessary dislocations, are reported to influence the redox reactions in battery particles through single‐particle, multimodal, and in situ synchrotron measurements. Through Laue X‐ray microdiffraction, many crystallographic defects are spatially identified and statistically quantified from a large quantity of diffraction patterns in many layered oxide particles, including geometrically necessary dislocations, tilt boundaries, and mixed defects. The in situ and ex situ measurements, combining microdiffraction and X‐ray spectroscopy imaging, reveal that LiCoO2particles with a higher concentration of geometrically necessary dislocations provide deeper charging reactions, indicating that dislocations may facilitate redox reactions in layered oxides during initial charging. The present study illustrates that a precise control of crystallographic defects and their distribution can potentially promote and homogenize redox reactions in battery materials.
-
more » « less
Abstract Solid–gas interactions at electrode surfaces determine the efficiency of solid‐oxide fuel cells and electrolyzers. Here, the correlation between surface–gas kinetics and the crystal orientation of perovskite electrodes is studied in the model system La0.8Sr0.2Co0.2Fe0.8O3. The gas‐exchange kinetics are characterized by synthesizing epitaxial half‐cell geometries where three single‐variant surfaces are produced [i.e., La0.8Sr0.2Co0.2Fe0.8O3/La0.9Sr0.1Ga0.95Mg0.05O3−δ/SrRuO3/SrTiO3(001), (110), and (111)]. Electrochemical impedance spectroscopy and electrical conductivity relaxation measurements reveal a strong surface‐orientation dependency of the gas‐exchange kinetics, wherein (111)‐oriented surfaces exhibit an activity >3‐times higher as compared to (001)‐oriented surfaces. Oxygen partial pressure ()‐dependent electrochemical impedance spectroscopy studies reveal that while the three surfaces have different gas‐exchange kinetics, the reaction mechanisms and rate‐limiting steps are the same (i.e., charge‐transfer to the diatomic oxygen species). First‐principles calculations suggest that the formation energy of vacancies and adsorption at the various surfaces is different and influenced by the surface polarity. Finally, synchrotron‐based, ambient‐pressure X‐ray spectroscopies reveal distinct electronic changes and surface chemistry among the different surface orientations. Taken together, thin‐film epitaxy provides an efficient approach to control and understand the electrode reactivity ultimately demonstrating that the (111)‐surface exhibits a high density of active surface sites which leads to higher activity.
